US8673546B2 - Process for forming a hydrophilic coating and hydrophilic coating, and process for forming an ink jet recording head and ink jet recording head - Google Patents
Process for forming a hydrophilic coating and hydrophilic coating, and process for forming an ink jet recording head and ink jet recording head Download PDFInfo
- Publication number
- US8673546B2 US8673546B2 US13/281,124 US201113281124A US8673546B2 US 8673546 B2 US8673546 B2 US 8673546B2 US 201113281124 A US201113281124 A US 201113281124A US 8673546 B2 US8673546 B2 US 8673546B2
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- United States
- Prior art keywords
- acid
- photoacid generator
- forming
- resin layer
- coating resin
- Prior art date
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- Expired - Fee Related, expires
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- 238000000034 method Methods 0.000 title claims abstract description 92
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- AQTIRDJOWSATJB-UHFFFAOYSA-K antimonic acid Chemical compound O[Sb](O)(O)=O AQTIRDJOWSATJB-UHFFFAOYSA-K 0.000 claims abstract description 46
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- 150000001875 compounds Chemical class 0.000 claims description 21
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- 150000002148 esters Chemical class 0.000 claims description 4
- 239000010410 layer Substances 0.000 description 167
- 239000002344 surface layer Substances 0.000 description 27
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- 238000003776 cleavage reaction Methods 0.000 description 7
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Images
Classifications
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- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1606—Coating the nozzle area or the ink chamber
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1601—Production of bubble jet print heads
- B41J2/1603—Production of bubble jet print heads of the front shooter type
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1626—Manufacturing processes etching
- B41J2/1629—Manufacturing processes etching wet etching
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1631—Manufacturing processes photolithography
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/1637—Manufacturing processes molding
- B41J2/1639—Manufacturing processes molding sacrificial molding
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41J—TYPEWRITERS; SELECTIVE PRINTING MECHANISMS, i.e. MECHANISMS PRINTING OTHERWISE THAN FROM A FORME; CORRECTION OF TYPOGRAPHICAL ERRORS
- B41J2/00—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed
- B41J2/005—Typewriters or selective printing mechanisms characterised by the printing or marking process for which they are designed characterised by bringing liquid or particles selectively into contact with a printing material
- B41J2/01—Ink jet
- B41J2/135—Nozzles
- B41J2/16—Production of nozzles
- B41J2/1621—Manufacturing processes
- B41J2/164—Manufacturing processes thin film formation
- B41J2/1645—Manufacturing processes thin film formation thin film formation by spincoating
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/20—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the epoxy compounds used
- C08G59/32—Epoxy compounds containing three or more epoxy groups
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G59/00—Polycondensates containing more than one epoxy group per molecule; Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups
- C08G59/18—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing
- C08G59/68—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used
- C08G59/687—Macromolecules obtained by polymerising compounds containing more than one epoxy group per molecule using curing agents or catalysts which react with the epoxy groups ; e.g. general methods of curing characterised by the catalysts used containing sulfur
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D163/00—Coating compositions based on epoxy resins; Coating compositions based on derivatives of epoxy resins
Definitions
- the present invention relates to a process for forming a hydrophilic coating and a hydrophilic coating formed by such process, and a process for forming an ink jet recording head including the hydrophilic coating and an ink jet recording head formed by such process.
- a technology for performing patterning by processing a resin composition by photolithography is applied in a variety of fields.
- Examples of the technology include a process for forming an ink jet recording head.
- An ink jet recording head for performing recording by ejecting ink onto a recording medium generally includes multiple fine ink ejection orifices, ink flow paths, and energy generating elements for generating energy necessary for ejecting ink to be provided in parts of the ink flow paths.
- Japanese Examined Patent Publication No. H06-45242 describes a process of producing such ink jet recording head.
- an ink flow path pattern is formed with a soluble resin on a substrate having energy generating elements formed thereon.
- a coating resin layer including a cationic polymerization resin and a photoacid generator is formed on the ink flow path pattern, and ink ejection orifices are formed above the energy generating elements by photolithography.
- the soluble resin is dissolved and the coating resin layer is then cured to form an ink flow path member.
- ink to be ejected from ink ejection orifices be constantly ejected in a vertical direction with respect to an ink ejection orifice surface.
- ink to be ejected is attracted into the ink pool, and the flying direction of each of ink droplets deviates from the normal direction, with the result that normal ejection is not achieved in some cases.
- Japanese Patent Application Laid-Open No. H06-122210 describes those surface treatment processes.
- examples of the process for subjecting an ink ejection orifice surface to water-repellent treatment include a process including applying a fluorine-based water repellent.
- examples of the process for subjecting an ink ejection orifice surface to hydrophilic treatment include a process including performing hydrophilization by generating a polar group in the ink ejection orifice surface by acid treatment, plasma treatment, or the like.
- the conventional processes each require an apparatus exclusively used for acid treatment, plasma treatment, or the like in the formation of a hydrophilic coating, and the hydrophilic coating cannot be formed with a photolithography apparatus alone, with the result that a large burden is imposed in some cases.
- An object of the present invention is to provide a process for forming a hydrophilic coating easily by photolithography without requiring any apparatus exclusively used for hydrophilic treatment and a hydrophilic coating formed by the process.
- Another object of the present invention is to provide a process for forming an ink jet recording head including the hydrophilic coating and an ink jet recording head formed by the process.
- a process for forming a hydrophilic coating having a hydrophilized surface includes the steps of:
- the present invention also provides a hydrophilic coating, which is obtained by the process for forming a hydrophilic coating, in which a surface of the hydrophilic coating has a polar group generated by cleavage of the cationic polymerization resin, and the surface has a static contact angle with pure water of 20° or less.
- the present invention also provides a process for forming an ink jet recording head including: a substrate having energy generating elements formed thereon for generating energy necessary for ejecting ink; and an ink flow path member, which forms ejection orifices for ejecting ink and an ink flow path communicating with the ejection orifices and holding ink, and which is hydrophilized in its surface having the ejection orifices, the process including the steps of:
- the present invention also provides an ink jet recording head, which is obtained by the process for forming an ink jet recording head, in which a surface having the ejection orifices has a polar group generated by cleavage of the cationic polymerization resin, and the surface having the ejection orifices has a static contact angle with pure water of 20° or less.
- FIG. 1 is a schematic cross-sectional view of a hydrophilic coating formed by a process for forming a hydrophilic coating according to the present invention.
- FIGS. 2A , 2 B, 2 C, 2 D and 2 E are views for illustrating the respective steps of the process for forming a hydrophilic coating according to the present invention.
- FIG. 3 is a graph showing remaining ether ratios in hydrophilic coating surfaces including cationic polymerization resins.
- FIG. 4 is a graph showing contact angles of hydrophilic coating surfaces including cationic polymerization resins.
- FIG. 5 is a graph showing thicknesses of hydrophilic coatings including cationic polymerization resins.
- FIG. 6 is a schematic view of an ink jet recording head formed by a process for forming an ink jet recording head according to the present invention.
- FIG. 7 is a schematic cross-sectional view of an ink jet recording head, which has an ink supply member and is formed by the process for forming an ink jet recording head according to the present invention.
- FIGS. 8A , 8 B, 8 C, 8 D, 8 E, 8 F, 8 G and 8 H are views for illustrating the respective steps of the process for forming an ink jet recording head according to the present invention.
- the inventor of the present invention has made intensive studies in order to solve the above-mentioned problems. As a result, the inventor has found a process for forming a hydrophilic coating by generating a polar group in a surface of a coating resin layer including a specific cationic polymerization resin and a specific photoacid generator by photolithography.
- the “hydrophilic coating” as used herein refers to a coating having a static contact angle with pure water of 20° or less.
- the hydrophilic coating can be formed easily by conventional photolithography without requiring any apparatus exclusively used for hydrophilic treatment.
- the process for forming a hydrophilic coating according to the present invention is applicable to a process for forming semiconductor, an MEMS field, and the like as well as a process for forming an ink jet recording head.
- the process for forming a hydrophilic coating according to the present invention includes the steps of:
- a photoacid generator holding layer including a photoacid generator (photoacid generator B) which generates an acid having a stronger acid strength than that of antimonic acid by irradiation with the active energy ray, and a holder, which holds the photoacid generator and can be removed in the step (3);
- FIG. 1 illustrates an example of a hydrophilic coating formed by the process for forming a hydrophilic coating according to the present invention.
- a substrate is represented by reference numeral 1 and a coating having a hydrophilized surface (hydrophilic coating) is represented by reference numeral 2 d .
- the hydrophilic coating 2 d has a cured coating resin layer 2 b and a hydrophilic layer 2 c on its surface.
- the process for forming a hydrophilic coating of FIG. 1 is described with reference to FIGS. 2A to 2E .
- the present invention is not limited thereto.
- a coating resin layer 2 a including a cationic polymerization resin and a photoacid generator A is formed on a substrate 1 ( FIG. 2A ).
- the coating resin layer 2 a may be formed directly on a surface of the substrate 1 , or alternatively, any other layer (for example, positive photosensitive resin layer) may be provided between the substrate 1 and the coating resin layer 2 a .
- the cationic polymerization resin may be any such compound that includes an acid-cleavable linkage such as an ether linkage or an ester linkage in its main chain as represented, for example, by each of the following formula 1-a to the following formula 1-i.
- the “main chain” means a chain which serves as a backbone in a carbon skeleton of a chain compound and has the maximum number of carbon atoms.
- l, m, and n each independently represent an integer of 1 or more.
- a cationic polymerization resin as represented by each of the following formula 2-a to the following formula 2-e is defined as being free of an ether linkage in its main chain in the present invention.
- n represents an integer of 1 or more.
- the photoacid generator A contained in the coating resin layer 2 a may be any photoacid generator which generates antimonic acid or an acid having a weaker acid strength than that of antimonic acid by irradiation with an active energy ray including light, more specifically ultraviolet light.
- the acid strength of the acid generated from the photoacid generator is described with reference to Table 1 below.
- Table 1 is an example showing photoacid generators and the order of the acid strengths of acids generated from the photoacid generators.
- the strength of the acid generated from the photoacid generator may be measured by the following process. That is, the strength may be measured by using resin compositions including the same kind of cationic polymerization resin and the same addition amount (molar number) of photoacid generators, and comparing exposure amounts required for forming a certain pattern by photolithography. It can be said that the smaller exposure amount indicates that the photoacid generator generates an acid having a stronger acid strength.
- the order of the acid strengths is the order of methide acid>antimonic acid>phosphoric acid>acetic acid.
- examples of the photoacid generator A included in the coating resin layer 2 a include a photoacid generator which generates antimonic acid.
- the photoacid generator which generates antimonic acid has a structure represented by the following formula 3 as an anion moiety. SbF 6 ⁇ Formula 3
- photoacid generator which generates antimonic acid are represented by the following formula 4-a to the following formula 4-j, respectively.
- the photoacid generator A there may also be used, for example, a compound obtained by changing the anion moiety (SbF 6 ⁇ ) of the compound represented by each of the above-mentioned formula 4-a to formula 4-j to PF 6 ⁇ or CH 3 COO ⁇ .
- a process for forming the coating resin layer 2 a is, for example, the following process. That is, the process is a process including applying a solution which is obtained by appropriately dissolving materials for the coating resin layer 2 a (including a cationic polymerization resin and a photoacid generator A) in a solvent, onto the substrate 1 by a spin coating process. It should be noted that the materials for the coating resin layer 2 a may also be applied onto the substrate 1 without using any solvent, but in the case of using a solvent, the solvent is appropriately selected from solvents which do not dissolve the substrate 1 and used.
- the coating resin layer 2 a may include a functionality-imparting material such as an ultraviolet absorber or a silane coupling agent in addition to the above-mentioned cationic polymerization resin and photoacid generator A.
- a functionality-imparting material such as an ultraviolet absorber or a silane coupling agent
- the content of the cationic polymerization resin in the coating resin layer 2 a is preferably about 50 mass % or more with respect to the total amount in the case of using a solvent from the viewpoint of coating property.
- the content of the photoacid generator A in the coating resin layer 2 a is preferably about 1 mass % with respect to the cationic polymerization resin from the viewpoint of reactivity.
- a photoacid generator holding layer 3 including a photoacid generator B and a holder which holds the photoacid generator B and can be removed in the step (3) to be described later is laminated on the coating resin layer 2 a ( FIG. 2B ).
- the photoacid generator B included in the photoacid generator holding layer 3 may be any photoacid generator which generates an acid having a stronger acid strength than that of antimonic acid by irradiation with an active energy ray including ultraviolet light.
- Examples of the photoacid generator B include a photoacid generator which generates methide acid.
- the photoacid generator which generates methide acid has a structure represented by the following formula 5 as an anion moiety.
- photoacid generator which generates methide acid are represented by the following formula 6-a to the following formula 6-j, respectively.
- the holder may be any holder which can hold the photoacid generator B in the surface layer of the coating resin layer 2 a and which can be removed in the subsequent step (3), i.e., is removed through development treatment in the step (3), and may be a monomer or a polymer. Examples thereof include a novolac resin and a cyclized rubber which do not undergo any cationic polymerization (crosslinking) reaction.
- the “surface layer of the coating resin layer 2 a ” means a surface on which a hydrophilic layer is formed.
- a process for forming the photoacid generator holding layer 3 is, for example, the following process. That is, the process is a process including applying a solution which is obtained by appropriately dissolving materials for the photoacid generator holding layer 3 (including a holder and a photoacid generator B) in a solvent, onto the coating resin layer 2 a by a spin coating process. It should be noted that the materials for the photoacid generator holding layer 3 may also be applied onto the coating resin layer without using any solvent, but in the case of using a solvent, the solvent is appropriately selected from solvents which do not dissolve the coating resin layer 2 a and used.
- the thickness of the photoacid generator holding layer 3 is not particularly limited as long as the removability is not impaired, but is desirably 3 ⁇ m or less in terms of a thickness on the coating resin layer 2 a.
- the cured coating resin layer is represented by reference numeral 2 b.
- FIG. 2D an acid (not shown) generated from the photoacid generator B derived from the photoacid generator layer 3 has been impregnated into the surface layer of the cured coating resin layer 2 b.
- a hydrophilic layer 2 c is formed on the surface layer of the cured coating resin layer 2 b through heat treatment of the surface layer ( FIG. 2E ).
- the heat treatment may be, for example, treatment in an oven or treatment on a hot plate.
- the heat treatment may be carried out at any temperature as long as the acid generated from the photoacid generator B derived from the photoacid generator holding layer 3 , which has been impregnated into the surface layer of the cured coating resin layer 2 b , can cause acid cleavage of the cationic polymerization resin in the surface layer to generate a polar group, hydrophilize the surface layer, and form the hydrophilic layer 2 c.
- the number of ethers is expressed as a ratio of an ether-derived peak intensity when measured with a Fourier transform infrared spectrophotometer (FT-IR) to a peak intensity as a reference. It should be noted that the peak intensity as a reference used here is that of a CH group.
- FT-IR Fourier transform infrared spectrophotometer
- the combination is a combination of No. 1 described in Table 2, and is a combination including a cationic polymerization resin (1-a), which has an acid-cleavable linkage in its main chain, and a photoacid generator (6-a), which generates an acid having a stronger acid strength than that of antimonic acid, in the coating resin layer.
- No. 3 of Table 2, i.e., a combination including the cationic polymerization resin (1-a) and a photoacid generator (4-a), which generates antimonic acid, in the coating resin layer does not show a decrease in number of ethers in the surface layer of the coating resin layer due to heat treatment. That is, this indicates that the cationic polymerization resin which includes an acid-cleavable linkage in its main chain does not undergo acid cleavage by antimonic acid. That is, this indicates that the standard for the acid strength necessary for the acid cleavage of the cationic polymerization resin is antimonic acid.
- FIG. 4 shows a correlation between the heat treatment temperatures and the static contact angles with pure water of surfaces of hydrophilic coatings, the hydrophilic coatings being each obtained by directly forming, on a substrate, the coating resin layer including the cationic polymerization resin and the photoacid generator each described in Table 2 and subjecting the layer to exposure and heat treatment.
- the contact angle decreases depending on a decrease in number of remaining ethers in the surface layer of the coating resin layer.
- the static contact angle with pure water of the hydrophilic coating surface was measured using a contact angle meter (trade name: “FACE CA-XA150” manufactured by Kyowa Interface Science Co., Ltd.). The measurement limit of the method of measuring the contact angle carried out here is 20° or less.
- the surface layer of the coating resin layer including the cationic polymerization resin is easily hydrophilized at a heat treatment temperature of 160° C. or more.
- the combination is a combination of No. 1 of Table 2 including the cationic polymerization resin (1-a), which has an acid-cleavable linkage in its main chain, and the photoacid generator (6-a), which generates an acid having a stronger acid strength than that of antimonic acid, in the coating resin layer.
- FIG. 5 shows a correlation between the heat treatment temperatures and the thicknesses of the hydrophilic coatings formed with the combinations described in Table 2.
- the thickness of the coating resin layer before heat treatment was 20 ⁇ m.
- the resin thickness decreases depending on a decrease in number of remaining ethers in the surface layer of the coating resin layer. That is, this indicates that not only the ether linkage in the surface layer of the resin but also the ether linkage in the resin is cleaved. In this case, there is a risk of a reduction in reliability of the resin layer such as a reduction in adherence between the resin layer and the substrate.
- such cationic polymerization resin which has an acid-cleavable linkage as represented, for example, by each of the formula 1-a to the formula 1-i is used in a coating resin layer, and on the coating resin layer, a photoacid generator layer including the photoacid generator B which generates an acid having a strong acid strength as represented, for example, by each of the formula 6-a to the formula 6-j is laminated.
- a photoacid generator layer including the photoacid generator B which generates an acid having a strong acid strength as represented, for example, by each of the formula 6-a to the formula 6-j is laminated.
- the upper limit of the heat treatment temperature in the step (4) is preferably 250° C. or less in consideration of heat decomposition of the coating resin layer 2 b cured in the step (3).
- a process for forming an ink jet recording head is a process for forming an ink jet recording head including: a substrate having energy generating elements formed thereon for generating energy necessary for ejecting ink; and an ink flow path member, which forms ejection orifices for ejecting ink and an ink flow path communicating with the ejection orifices and holding ink, and which is hydrophilized in its surface having the ejection orifices. Further, the process includes the steps of:
- FIG. 6 illustrates an example of an ink jet recording head formed by the process for forming an ink jet recording head according to the present invention.
- the ink jet recording head illustrated in FIG. 6 has an ink flow path member 7 d having a hydrophilized surface layer, i.e., a hydrophilic coating (the surface layer is a hydrophilic layer 7 c ) on a substrate 4 having thereon multiple energy generating elements 5 for generating energy necessary for ejecting ink.
- the ink flow path member 7 d forms ink ejection orifices 10 for ejecting ink and an ink flow path 6 b communicating with the ink ejection orifices 10 and holding ink.
- the substrate 4 is provided with an ink supply port 11 for supplying ink to the ink flow path 6 b .
- FIG. 7 is a view illustrating a cross-section taken along the line 7 - 7 of FIG. 6 of an ink jet recording head having an ink supply member 12 adhered to the back surface of the substrate 4 in the ink jet recording head of FIG. 6 .
- the multiple energy generating elements 5 are arranged on the substrate 4 in two arrays at a given pitch. It should be noted that control signal input electrode (not shown) for driving the energy generating elements 5 is connected to the elements.
- FIGS. 8B to 8H are step-by-step cross-sectional views each corresponding to the cross-section taken along the line 7 - 7 of FIG. 6 .
- a positive photosensitive resin layer (not shown) including a positive photosensitive resin is formed on the substrate 4 having the energy generating elements 5 formed thereon.
- An ink flow path pattern 6 a may be formed by patterning the positive photosensitive resin layer as necessary like a step (a2) to be described later.
- the positive photosensitive resin included in the positive photosensitive resin layer is not particularly limited, but preferred is a material having a low absorbance for ultraviolet light used for exposure of a coating resin layer 7 a to be described later. Also preferred is a material sensitive to an active energy ray having a shorter wavelength than that of the ultraviolet light to be used, for example, excimer laser such as ArF laser or KrF laser, or Deep UV light. Examples of the material include polymethyl isopropenyl ketone, which can be exposed to Deep UV light.
- a process for forming the positive photosensitive resin layer is, for example, the following process. First, the positive photosensitive resin is appropriately dissolved in a solvent and applied by a spin coating process. After that, the resultant may be subjected to prebaking to form the positive photosensitive resin layer.
- the thickness of the positive photosensitive resin layer may be appropriately selected depending on a desired ink flow path height without any particular limitation, but is preferably 5 ⁇ m or more and 20 ⁇ m or less.
- the ink flow path pattern 6 a is formed by patterning the positive photosensitive resin layer ( FIG. 8B ).
- a process for patterning the positive photosensitive resin layer is, for example, the following process.
- the positive photosensitive resin layer is irradiated via a mask with an active energy ray capable of photosensitizing the positive photosensitive resin to perform pattern exposure.
- the layer may be developed with, for example, a solvent capable of dissolving the positive photosensitive resin and subjected to rinsing treatment to form the ink flow path pattern 6 a.
- Step (a3) Corresponding to Step (I)
- the coating resin layer 7 a including a cationic polymerization resin and a photoacid generator A is formed on the ink flow path pattern 6 a and the substrate 4 ( FIG. 8C ).
- the cationic polymerization resin may be any cationic polymerization resin which has an acid-cleavable linkage such as an ether linkage or an ester linkage in its main chain, and examples thereof include the compound represented, for example, by each of the formula 1-a to the formula 1-i as described above.
- the photoacid generator A may be any photoacid generator which generates antimonic acid or an acid having a weaker acid strength than that of antimonic acid by irradiation with an active energy ray including ultraviolet light, and examples thereof include the compound represented, for example, by each of the formula 4-a to the formula 4-j as described above.
- a process for forming the coating resin layer 7 a is, for example, the following process. That is, the process is a process including applying a solution which is obtained by appropriately dissolving materials for the coating resin layer 7 a in a solvent, onto the ink flow path pattern 6 a and the substrate 4 by a spin coating process. It should be noted that the solvent for dissolving the materials for the coating resin layer 7 a may be appropriately selected from solvents which do not dissolve the ink flow path pattern 6 a and used.
- the thickness of the coating resin layer 7 a is preferably 3 ⁇ m or more in terms of a thickness on the ink flow path pattern 6 a (distance from the surface of the coating resin layer to the ink flow path pattern 6 a ) in consideration of the strength of the resin layer. Further, the upper limit of the thickness is not particularly limited as long as the developability at an ink ejection orifice portion is not impaired, but is preferably 50 ⁇ m or less in terms of a thickness on the ink flow path pattern 6 a.
- Step (a4) Corresponding to Step (II)
- a photoacid generator holding layer 8 including a holder and a photoacid generator B is laminated on the coating resin layer 7 a ( FIG. 8D ).
- the photoacid generator B may be any photoacid generator which generates an acid having a stronger acid strength than that of antimonic acid by irradiation with an active energy ray including ultraviolet light, and examples thereof include such compounds as represented by the formula 6-a to the formula 6-j as described above.
- the holder for the photoacid generator B may be any holder which can hold the photoacid generator B in the surface layer of the coating resin layer 7 a and which can be removed through development treatment in the subsequent step (a5), and may be a monomer or a polymer. Examples thereof include a novolac resin and a cyclized rubber.
- a process for forming the photoacid generator holding layer 8 is, for example, the following process. That is, the process is a process including applying a solution which is obtained by appropriately dissolving materials for forming the photoacid generator holding layer in a solvent, onto a coating resin layer by a spin coating process.
- a solvent for dissolving the materials for forming the photoacid generator holding layer may be appropriately selected from solvents which do not dissolve the coating resin layer 7 a and used.
- the thickness of the photoacid generator holding layer 8 is not particularly limited as long as the removability is not impaired and ink ejection orifices can be formed, but is desirably 3 ⁇ m or less in terms of a thickness on the coating resin layer 7 a.
- Step (a5) Corresponding to Step (III)
- ink ejection orifices 10 are formed by removing the photoacid generator holding layer 8 and curing the coating resin layer 7 a through exposure of the coating resin layer 7 a and the photoacid generator holding layer 8 to an active energy ray including ultraviolet light to conduct development ( FIGS. 8E and 8F ).
- a process for forming the ink ejection orifices is, for example, the following process.
- the coating resin layer 7 a and the photoacid generator holding layer 8 are irradiated with the i-line as an active energy ray via a mask 9 corresponding to the shape of each of the ink ejection orifices 10 .
- the photoacid generator holding layer 8 may be removed through heating, development, and rinsing treatment to form the ink ejection orifices 10 .
- FIG. 8F an acid (not shown) generated from the photoacid generator B derived from the photoacid generator layer 8 has been impregnated into the surface layer of the cured coating resin layer 7 b.
- each of the ink ejection orifices 10 may be appropriately set depending on the size of each of ink droplets to be ejected.
- an ink supply port 11 is formed by etching.
- the ink flow path pattern 6 a is removed to form an ink flow path 6 b ( FIG. 8G ).
- a process for removing the ink flow path pattern 6 a is, for example, a process including removing the ink flow path pattern 6 a by immersing the substrate in a solvent capable of dissolving the ink flow path pattern. Further, as necessary, the ink flow path pattern 6 a may be exposed to an active energy ray capable of photosensitizing the ink flow path pattern to enhance the solubility.
- Step (a7) Corresponding to Step (IV)
- a hydrophilic layer 7 c is formed on a surface layer of the coating resin layer 7 b cured through heat treatment ( FIG. 8H ).
- the heat treatment may be carried out at any temperature as long as an acid generated from the photoacid generator B derived from the photoacid generator holding layer 8 impregnated into the surface layer of the cured coating resin layer 7 b can cause acid cleavage of the cationic polymerization resin in the surface layer of the cured coating resin layer 7 b to generate a polar group and hydrophilize the surface layer.
- the temperature is preferably 160° C. or more as described above.
- the heat treatment temperature is preferably 250° C. or less in consideration of physical properties of the coating resin layer as described above.
- the ink flow path surface preferably has a static contact angle with pure water of 50° or more.
- the “ink flow path surface” as used herein refers to a surface on the ink flow path 6 b side of the ink flow path member 7 d , and the contact angle at this site may be measured as a static contact angle with pure water by peeling the ink flow path member 7 d from the substrate 4 , for example.
- the contact angle with pure water is preferably 50° or more and preferably 70° or less in consideration of the efficient refilling of ink and the stability of meniscus oscillation of ink after the refilling.
- the energy generating elements 5 are electrically joined in order to drive the elements.
- an ink supply member 12 for supplying ink and the like are connected.
- an ink jet recording head is completed ( FIG. 7 ).
- the ink jet recording head according to the present invention is mountable to apparatuses such as a printer, a copier, a facsimile having a communication system, and a word processor having a printer unit, and industrial recording apparatuses integrally combined with various processing apparatuses. Further, the use of the ink jet recording head of the present invention allows recording in a variety of recording media made of paper, yarn, fiber, leather, metal, plastic, glass, wood, ceramic, and the like.
- a surface having ink ejection orifices (ink ejection orifice surface: reference numeral 13 of FIG. 8H ) of an ink jet recording head produced in each of Examples was measured for its static contact angle with pure water using a contact angle meter (trade name: “FACE CA-XA150” manufactured by Kyowa Interface Science Co., Ltd.).
- An ink jet recording head produced in each of Examples and Comparative Examples was immersed in ink having the following composition at 60° C. for 1 week and then evaluated for its adherence between an ink flow path member 7 d and a substrate 4 .
- polymethyl isopropenyl ketone (trade name: “ODUR-1010” manufactured by TOKYO OHKA KOGYO CO., LTD.) as a positive photosensitive resin was applied onto a silicon substrate 4 having electrothermal transducing elements 5 formed thereon as energy generating elements by spin coating.
- the silicon substrate was subjected to prebaking at 120° C. for 6 minutes.
- pattern exposure of an ink flow path pattern 6 a (exposure amount: 14 J/cm 2 ) was carried out with a Deep UV exposing machine (trade name: “UX-3000” manufactured by Ushio Inc.).
- the ink flow path pattern 6 a was formed ( FIG. 8B ). It should be noted that the ink flow path pattern 6 a had a thickness of 10 ⁇ m.
- the following resin composition 1 was dissolved at a concentration of 50 mass % in a mixed solvent of methyl isobutyl ketone and diethylene glycol monomethyl ether.
- the solution was applied onto the ink flow path pattern 6 a and the silicon substrate 4 by spin coating, thereby forming a coating resin layer 7 a ( FIG. 8C ).
- the thickness of the coating resin layer 7 a on the ink flow path pattern 6 a was 10 ⁇ m.
- EHPE-3150 (trade name: manufactured by DAICEL CHEMICAL INDUSTRIES, LTD., compound represented by the formula 1-a): 100 parts by mass
- the following photoacid generator B-1 was dissolved at a concentration of 1 mass % in a novolac resin resist as a holder.
- the solution was applied onto a coating resin layer 7 a by spin coating to form a photoacid generator holding layer 8 ( FIG. 8D ). It should be noted that the thickness of the photoacid generator holding layer 8 on the coating resin layer 7 a was 1 ⁇ m.
- the coating resin layer 7 a and the photoacid generator holding layer 8 were exposed (exposure amount: 4,000 J/m 2 ) via a mask 9 corresponding to the shape of each of ink ejection orifices 10 using an i-line stepper exposing machine (i5 manufactured by Canon Inc.) ( FIG. 8E ).
- the layers were subjected to post-exposure baking (PEB) at 90° C. for 4 minutes, development with methyl isobutyl ketone, and rinsing treatment with IPA.
- PEB post-exposure baking
- the photoacid generator holding layer 8 was removed and the coating resin layer 7 a was cured to form the ink ejection orifices 10 ( FIG. 8F ).
- the cured coating resin layer is represented by reference numeral 7 b . It should be noted that any of the ink ejection orifices 10 had a diameter of 10 ⁇ m. Further, an acid generated from the photoacid generator B-1 had been impregnated into the surface layer of the coating resin layer 7 b cured at this time.
- the substrate was subjected to etching in tetramethylammonium hydroxide (TMAH) to form an ink supply port 11 .
- TMAH tetramethylammonium hydroxide
- the resultant was exposed (exposure amount: 27 J/cm 2 ) again with the Deep UV exposing apparatus (trade name: “UX-3000” manufactured by Ushio Inc.) used in forming the ink flow path pattern 6 a .
- the resultant was immersed in methyl lactate while being irradiated with an ultrasound to dissolve the remaining ink flow path pattern 6 a ( FIG. 8G ).
- hydrophilization was carried out by generating a polar group derived from the cationic polymerization resin on the cured coating resin layer 7 b by heating at 200° C. for 1 hour ( FIG. 8H ).
- an ink supply member 12 was bonded to the back surface of the silicon substrate 4 having formed therein the ink supply port 11 .
- an ink jet recording head was completed ( FIG. 7 ).
- Table 3 shows the evaluation results of the contact angle of the ink ejection orifice surface and the substrate adherence of the ink jet recording head.
- An ink jet recording head was produced and evaluated in the same manner as in Example 1 except that the following resin composition 2 was used in place of the resin composition 1.
- Table 3 shows the evaluation results.
- An ink jet recording head was produced and evaluated in the same manner as in Example 1 except that the following resin composition 3 was used in place of the resin composition 1. Table 3 shows the evaluation results.
- n represents an integer of 1 or more.
- An ink jet recording head was produced and evaluated in the same manner as in Example 1 except that the following photoacid generator B-2 was used in place of the photoacid generator B-1 included in the photoacid generator holding layer 8 .
- Table 3 shows the evaluation results.
- an ink jet recording head having an ink flow path member 7 d whose ink ejection orifice surface was subjected to hydrophilic treatment was able to be produced without impairing the adherence with the substrate 1 by Example 1 and Example 2.
- the process for easily forming a hydrophilic coating by photolithography without requiring any apparatus exclusively used for hydrophilic treatment, and the hydrophilic coating formed by the process. It is also possible to provide the process for forming an ink jet recording head including the hydrophilic coating and the ink jet recording head formed by the process.
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Abstract
Description
(2) laminating, on the coating resin layer, a photoacid generator holding layer including a photoacid generator, which generates an acid having a stronger acid strength than that of antimonic acid by irradiation with the active energy ray, and a holder, which holds the photoacid generator and can be removed in the step (3);
(3) removing the photoacid generator holding layer and curing the coating resin layer through exposure of the photoacid generator holding layer and the coating resin layer to the active energy ray to conduct development; and
(4) forming a hydrophilic coating by hydrophilizing a surface of the coating resin layer cured in the step (3) through heat treatment of the coating resin layer.
(II) laminating, on the coating resin layer, a photoacid generator holding layer including a photoacid generator, which generates an acid having a stronger acid strength than that of antimonic acid by irradiation with the active energy ray, and a holder, which holds the photoacid generator and can be removed in the step (III);
(III) forming the ejection orifices by removing the photoacid generator holding layer and curing the coating resin layer through exposure of the photoacid generator holding layer and the coating resin layer to the active energy ray to conduct development; and
(IV) forming the ink flow path member by hydrophilizing a surface having the ejection orifices of the coating resin layer cured in the step (III) through heat treatment of the coating resin layer.
(2) laminating, on the coating resin layer, a photoacid generator holding layer including a photoacid generator (photoacid generator B), which generates an acid having a stronger acid strength than that of antimonic acid by irradiation with the active energy ray, and a holder, which holds the photoacid generator and can be removed in the step (3);
(3) removing the photoacid generator holding layer and curing the coating resin layer through exposure of the photoacid generator holding layer and the coating resin layer to the active energy ray to conduct development; and
(4) forming a hydrophilic coating by hydrophilizing a surface of the coating resin layer cured in the step (3) through heat treatment of the coating resin layer.
TABLE 1 | |||
Exposure | Order of | ||
Acid | amount | acid | |
Photoacid generator | generated | (J/m2) | strengths |
|
Methide acid | 800 | 1 |
|
Antimonic acid | 2,500 | 2 |
|
Phosphoric acid | 20,000 | 3 |
|
Acetic acid | >30,000 | 4 |
SbF6 − Formula 3
TABLE 2 | |
Coating resin layer |
Cationic polymerization | ||
resin | Photoacid generator | |
No. 1 |
|
|
No. 2 |
|
|
No. 3 |
|
|
No. 4 |
|
|
(II) laminating, on the coating resin layer, a photoacid generator holding layer including a photoacid generator B, which generates an acid having a stronger acid strength than that of antimonic acid by irradiation with the active energy ray, and a holder, which holds the photoacid generator B and can be removed in the step (III);
(III) forming the ejection orifices by removing the photoacid generator holding layer and curing the coating resin layer through exposure of the photoacid generator holding layer and the coating resin layer to the active energy ray to conduct development; and
(IV) forming the ink flow path member by hydrophilizing a surface having the ejection orifices of the coating resin layer cured in the step (III) through heat treatment of the coating resin layer.
TABLE 3 | ||||
Contact | ||||
angle | ||||
Photoacid generator holding | with | |||
Coating resin layer | layer | pure | Substrate |
Cationic polymerization resin | Photoacid generator | Photoacid generator | water | adherence | |
Example 1 |
|
|
|
20° or less | No peeling |
Example 2 |
|
|
|
20° or less | No peeling |
Comparative Example 1 |
|
|
|
60° | No peeling |
Comparative Example 2 |
|
|
|
60° | No peeling |
Claims (12)
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JP2010250777A JP5697406B2 (en) | 2010-11-09 | 2010-11-09 | Hydrophilic film forming method, hydrophilic film, ink jet recording head manufacturing method, and ink jet recording head |
JP2010-250777 | 2010-11-09 |
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US20120115985A1 (en) | 2012-05-10 |
JP2012101162A (en) | 2012-05-31 |
JP5697406B2 (en) | 2015-04-08 |
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